CN111430730A - Preparation method of graphene modified carbon-based electrode and microbial electrochemical sewage treatment synchronous electricity generation device constructed by using same - Google Patents
Preparation method of graphene modified carbon-based electrode and microbial electrochemical sewage treatment synchronous electricity generation device constructed by using same Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
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Abstract
The invention provides a preparation method of a graphene modified carbon-based electrode and a microbial electrochemical sewage treatment synchronous power generation device constructed by using the same. The invention provides a microbial electrochemical device with a built-in graphene modified carbon-based electrode, wherein the graphene modified carbon-based electrode is prepared by electrochemically reducing graphene oxide and depositing the graphene oxide on the surface of a carbon-based material in situ. A continuous flow bioelectrochemical system is constructed by using a carbon-based electrode modified by graphene as a cathode and an anode, wherein activated sludge is inoculated to the anode, electrochemically active microorganisms are enriched on the surface of the electrode, the electric energy recovery can be enhanced while pollutants in water are degraded, and the output power density is more than 2 times that of a common carbon-based electrode. The invention also constructs a bioelectrochemical system with the built-in graphene modified carbon-based electrode, so that the resistance is reduced, the electric energy loss is reduced, and the sewage treatment and the electric energy recovery are enhanced.
Description
Technical Field
The invention relates to the field of bioelectrochemistry and sewage treatment, in particular to a microbial electrochemical system with a built-in graphene modified carbon-based electrode for strengthening sewage treatment and synchronously generating electricity.
Background
The bioelectrochemical systems (BESs) are a novel sewage treatment process, which utilizes the coupling of microbial reaction and electrochemical reaction, shows the advantages of rapidness and high efficiency in the aspect of removing pollutants in water, can recover electric energy while treating sewage, and is a sustainable sewage treatment technology.
At present, one of the limiting factors limiting the scale development of the BESs process is the problems of large impedance of the electrode, large energy consumption loss and low mass transfer efficiency, so that the search for suitable electrode materials or the improvement of the existing carbon-based materials is a breakthrough for strengthening the efficiency of the BESs and promoting the economic application of the BESs.
Graphene, a new member of carbon materials discovered in recent years, is a single-atom thick planar sheet composed of sp 2-bonded carbon atoms, densely arranged in a honeycomb lattice. Each atom has an s orbital and two in-plane p orbitals, contributing to the mechanical stability of the carbon sheet. It is the thinnest material known in the world, and conceptually constitutes the basic building block for many other carbon materials. Graphene has the unique properties of highest carrier mobility, high specific surface area, good electrochemical catalysis, high mechanical strength and the like, and therefore, is an ideal material for constructing electrodes.
Meanwhile, the graphene has good biocompatibility, and researches show that the graphene modified electrode can improve the performance of a bioelectrochemical system in the aspect of power generation. For example, the graphene is modified on a carbon cloth electrode and used as an anode, so that the enrichment of pseudomonas aeruginosa on the anode can be promoted, and the power density and the energy conversion efficiency of the power generation of the pseudomonas aeruginosa are respectively improved by 2.7 times and 3 times; the graphene powder is adhered to the stainless steel mesh by polytetrafluoroethylene, so that a graphene anode with a larger surface area can be constructed, more sites are provided for the attachment of escherichia coli, the overpotential of the anode is reduced, the electron transfer efficiency is improved, and the maximum power generation output is 18 times that of the stainless steel mesh under the same condition; when the graphene oxide is reduced at the anode of the bioelectrochemical system to form a mixture of graphene and microorganisms by using the respiration of Shewanella under the anaerobic or facultative anaerobic condition, the maximum power output of the bioelectrochemical system is improved by 32% compared with that of the anode without graphene, and when the graphene oxide is reduced at the cathode to form a mixture of graphene and microorganisms, the maximum power output of the bioelectrochemical system is improved by 103% compared with that of the cathode without graphene.
Based on the high conductivity and good biocompatibility of graphene, the invention provides a method for modifying a carbon-based electrode by graphene, and a continuous flow bioelectrochemical system is constructed by using the carbon-based electrode modified by graphene as a cathode and an anode, wherein activated sludge is inoculated to the anode, electrochemically active microorganisms are enriched on the surface of the electrode, the electric energy recovery can be enhanced while pollutants in water are degraded, and the output power density is more than 2 times that of a common carbon-based electrode. The invention aims to construct a bioelectrochemical system with a built-in graphene modified carbon-based electrode, reduce resistance, reduce electric energy loss and strengthen sewage treatment and electric energy recovery.
Disclosure of Invention
The invention aims to provide a microbial electrochemical system with a built-in graphene modified carbon-based electrode, which can degrade pollutants in sewage and enhance power generation.
In one aspect of the invention, a preparation method of a graphene modified carbon-based electrode is provided, which comprises the following steps:
(1) the graphene oxide solution is diluted by a buffer system with a pH of 6, wherein the buffer system can be: phosphate buffer, citrate buffer, acetate buffer, and the like;
(2) the concentration of the diluted graphene oxide is 0.3-0.5 mg/L
(3) Selecting a carbon-based electrode as a working electrode, wherein the carbon-based material can be selected from carbon cloth, carbon felt, carbon fiber and the like; before the carbon-based material is used, surface cleaning and pretreatment are carried out in an acid soaking and high-temperature treatment mode;
(4) select high conductive material for use as the counter electrode, high conductive material can select for use: platinum, glassy carbon, stainless steel mesh, etc.;
(5) constructing a three-electrode system by using the graphene oxide solution as an electrolyte;
(6) reducing graphene oxide in situ by using a cyclic voltammetry scanning method to obtain reduced graphene oxide (rGO), and synchronously depositing the reduced graphene oxide (rGO) on the surface of the carbon-based material; the scanning speed can be controlled at 50mV/s, and the scanning potential range is controlled at-1.6V-0.6 Vvs Ag/AgCl reference electrode.
And when the electrode system works, obtaining the graphene modified carbon-based electrode.
In another aspect of the present invention, there is provided a microbial electrochemical device with a built-in graphene-based electrode, including:
(1) the anode and the cathode are graphene-based electrodes;
(2) the anode electrolysis liquid system is sewage containing organic pollutants;
(3) a catholyte comprising one or more of: inorganic substances having a high oxidation state such as oxygen, potassium ferricyanide, nitrate, etc.; high oxidation state organic substances such as azo dyes, antibiotics, nitroaromatics and the like;
(4) the anode chamber and the cathode chamber are separated by a diaphragm, and the diaphragm can be formed by: membranes having ion selectivity such as cation exchange membranes, anion exchange membranes, proton exchange membranes, and the like;
(5) water is respectively fed into the anode chamber and the cathode chamber, and the anode chamber and the cathode chamber both run in a continuous flow mode;
(6) enriching an electrochemical active biological membrane on the surface of the electrode;
(7) the pollutants in the water are converted on the surface of the electrode through bioelectrochemical reaction, and current is generated, and the device finally outputs electric energy.
Compared with the prior art, the invention has the following advantages:
(1) the impedance is small. According to the invention, the graphene is used for modifying the carbon-based electrode material, so that the electrochemical activity and the electrode conductivity of the electrode are greatly improved, and the internal resistance and the charge transfer resistance of the microbial electrochemical device are greatly reduced.
(2) The sewage treatment efficiency is high. By utilizing the microbial electrochemical device with the built-in graphene-based electrode, the cathode and the anode can simultaneously treat sewage with two different water qualities, the pollutant degradation speed is high, and the removal efficiency is high.
(3) The electric energy conversion rate is high. The microbial electrochemical system with the built-in graphene-based electrode outputs electric energy while treating wastewater, and the power density is more than 2 times that of a common carbon-based electrode device.
Drawings
FIG. 1A is a scanning electron micrograph of a pretreated electrode material according to an embodiment of the present invention;
fig. 1B is a scanning electron microscope image of the graphene-modified carbon fiber electrode;
FIG. 2 is a graph of a graphene oxide reduction deposition curve of a cyclic voltammetric scan process according to an embodiment of the present invention;
FIG. 3 is a Raman spectrum of an electrode material and an unmodified carbon fiber electrode according to an embodiment of the present invention;
FIG. 4 is a cyclic voltammogram of an electrochemical characterization of an electrode material and an unmodified carbon fiber electrode of an embodiment of the invention;
FIG. 5 is a schematic view of a configuration of a microbial electrochemical device with a built-in graphene-modified carbon-based electrode according to an embodiment of the present invention;
FIG. 6 is a plot of current output versus time for a microbial electrochemical system in accordance with an embodiment of the present invention
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings in conjunction with specific embodiments.
One aspect of the embodiment of the invention provides a preparation method of a graphene-modified carbon-based electrode, in the embodiment, a citrate buffer system with the pH of 6.0 is selected, a 10 g/L graphene oxide solution is diluted to 0.5 g/L by using a citrate buffer solution and ultrasonically dispersed for 30min to form a stable colloid dispersion liquid, and a three-electrode system is constructed by using the graphene oxide solution as an electrolyte, a carbon fiber as a carbon-based electrode, a platinum mesh electrode as a counter electrode and Ag/AgCl as a reference electrode.
Soaking the carbon fiber electrode in 1 mol/L hydrochloric acid for 12h, washing with distilled water for 3 times, and treating at 450 deg.C for 30min in a muffle furnace to crack the surface of the carbon fiber, as shown in FIG. 1A.
Performing cyclic voltammetry scanning in a constructed three-electrode system through an electrochemical workstation, and performing graphene oxide reduction under the condition of continuous stirring, wherein the scanning range is-1.6-0.6V, the scanning speed is 50mV/s, the number of scanning circles is 40, the graphene oxide is continuously reduced on the surface of an electrode (as shown in figure 2) and is synchronously deposited on the surface of carbon fibers, the reduced graphene oxide is of a wrinkled lamellar structure, as shown in figure 1B, the lamellar structure comprises single-layer graphene or functionalized multi-layer graphene, and the thickness of the lamellar structure is nano-scale; raman spectrum measurement proves that the carbon fiber surface is modified by reduced graphene oxide, and the Raman spectrum is-1364 cm-1And-1610 cm-1The D peak and the G peak appear respectively, the intensity of the D peak and the G peak is obviously increased compared with that of the unmodified carbon fiber, and the intensity of the D peak and the G peak is 2710cm-1And 2913cm-1Respectively generating a typical characteristic peak 2D peak and a D + G peak of graphene; through cyclic voltammetry, as shown in fig. 4, the electrochemical activity of the carbon fiber electrode modified with graphene is increased, the redox current is significantly increased, and the electroactive area of the carbon fiber electrode modified with graphene is increased by more than 2 times through measurement and calculation. These results prove that the graphene oxide can form reduced graphene oxide to be modified on the surface of the carbon fiber through electrochemical reduction, so that the electrochemical activity of the carbon fiber electrode is improved, the conductivity is improved, the resistance of the electrode is reduced, and the process energy consumption is reduced.
The prepared electrode can be applied to the field of bioelectrochemistry, and in another aspect of the embodiment of the present invention, there is also provided a continuous flow bioelectrochemical electricity generation apparatus, as shown in fig. 5, the apparatus including:
the anode chamber and the cathode chamber are both 100m L in the volume ratio of 1:1, the anode chamber and the cathode chamber are both provided with a water inlet, a water outlet, an internal circulation port and a reference electrode port, the interfaces are designed as through-plate interfaces, the anode chamber and the cathode chamber are separated by a cation exchange membrane, the electrode materials of the anode and the cathode are carbon fibers modified with graphene, activated sludge is inoculated to the anode, the inlet water contains sodium acetate (2 g/L) and is used as a carbon source for the growth of anode microorganisms, the anode performs an acetic acid oxidation reaction, the cathode continuously contains potassium ferricyanide (0.1 mol/L) and performs a reaction of reducing ferric iron into ferrous iron, and a 1000 ohm resistor is loaded between the cathode and the anode and is used for collecting circuit current.
In this example, the anode chamber is in an intermittent water inlet mode, the water inlet period is 96 hours, and the cathode is in a continuous water inlet mode, and the result shows that the bioelectrochemical device starts to output electric energy after 72 hours, as shown in fig. 6, the voltage changes in a period every 96 hours, and the peak voltage reaches 0.7V; and the starting time of the device with the unmodified graphene electrode is as long as 500h, and the peak voltage value is only 0.55V. After 2000 hours of continuous and stable operation, the electrode performance is kept stable all the time, the degradation efficiency of organic matters in water reaches 98%, and a uniform biological film grows on the surface of the graphene-modified electrode through the observation of a scanning electron microscope, so that the effectiveness, stability and biocompatibility of the device for treating sewage are proved.
The results show that the electrochemical activity of the carbon fiber can be effectively improved by using the carbon fiber electrode modified by the graphene, and the electricity generation efficiency of the bioelectrochemical system with the carbon fiber electrode modified by the built-in graphene is obviously improved.
The above-mentioned embodiments are only examples of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphene modified carbon-based electrode is characterized by comprising the following steps:
(1) diluting a graphene oxide solution by using a buffer system with the pH value of 6.0, and taking the graphene oxide solution as an electrolyte, wherein the concentration of graphene oxide in the diluted electrolyte is 0.3-0.5 mg/L;
(2) selecting an unmodified carbon-based electrode as a working electrode;
(3) selecting a platinum electrode or a glassy carbon electrode as a counter electrode;
(4) constructing a three-electrode system by using the graphene oxide solution as an electrolyte;
(5) and reducing the graphene oxide in situ by using a cyclic voltammetry scanning method to obtain reduced graphene oxide, synchronously depositing the reduced graphene oxide on the surface of the carbon-based material, controlling the scanning rate of the cyclic voltammetry at a speed of 30-50 mV/s, and controlling the scanning potential range at-1.6V-0.6V vs Ag/AgCl reference electrode.
2. The method of claim 1, wherein the buffer system is: phosphate buffer, citrate buffer, or acetate buffer.
3. The method of claim 1, wherein the carbon-based electrode material is selected from carbon cloth, carbon felt, or carbon fiber.
4. The method according to claim 1, wherein the carbon-based electrode material is subjected to a non-smooth surface appearance by soaking the carbon-based electrode material for more than 12 hours in 0.1mol of hydrochloric acid and treating the carbon-based electrode material at 450 ℃ for more than 30min before use.
5. A microbial electrochemical system with a built-in graphene-based electrode is characterized in that:
(1) the anode and the cathode are graphene-based electrodes;
(2) the anode electrolysis liquid system is sewage containing organic pollutants;
(3) a catholyte comprising one or more of: oxygen, potassium ferricyanide, nitrates, azo dyes, antibiotics or nitroaromatics.
6. The system of claim 5, comprising an anode chamber and a cathode chamber, the volumes of the two compartments being adjustable.
7. The system of claim 6, wherein the anode chamber and the cathode chamber are separated by a membrane, and the membrane is a cation exchange membrane, an anion exchange membrane or a proton exchange membrane.
8. The system of claim 6 wherein the anode and cathode compartments are fed separately and are operated in continuous flow.
9. The system of claim 5, wherein electrochemically active microorganisms are grown on the surface of the electrode to form a biofilm.
10. The system of claim 5, wherein the contaminants in the water are converted at the electrode surface by a bioelectrochemical reaction and generate an electric current, and the device ultimately outputs electrical energy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114735806A (en) * | 2022-04-14 | 2022-07-12 | 北京工业大学 | Method for removing azo dye by graphene/polyaniline modified electrode enhanced bioelectrochemistry |
| CN115032253A (en) * | 2022-05-12 | 2022-09-09 | 北京理工大学 | Efficient electropolymerization L-arginine modified electrode and method for improving performance of microbial electrochemical system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479994A (en) * | 2021-07-14 | 2021-10-08 | 南开大学 | Graphene-magnetite conductive skeleton electrode, preparation method and application thereof, and method for treating petrochemical wastewater |
| CN114735806A (en) * | 2022-04-14 | 2022-07-12 | 北京工业大学 | Method for removing azo dye by graphene/polyaniline modified electrode enhanced bioelectrochemistry |
| CN115047046A (en) * | 2022-05-11 | 2022-09-13 | 北京工业大学 | Electrode biological carrier for one-step electrodeposition cross-lamination modification of graphene/polyaniline and preparation method thereof |
| CN115032253A (en) * | 2022-05-12 | 2022-09-09 | 北京理工大学 | Efficient electropolymerization L-arginine modified electrode and method for improving performance of microbial electrochemical system |
| CN118183983A (en) * | 2024-04-28 | 2024-06-14 | 重庆大学 | Method for removing pollutants in water by continuous flow multipath activation of peracetic acid |
| CN118183983B (en) * | 2024-04-28 | 2024-09-24 | 重庆大学 | Method for removing pollutants in water by continuous flow multipath activation of peracetic acid |
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